RU2531277C2 - Method of obtaining acrolein from glycerol or glycerine - Google Patents

Method of obtaining acrolein from glycerol or glycerine Download PDF

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RU2531277C2
RU2531277C2 RU2011123484/04A RU2011123484A RU2531277C2 RU 2531277 C2 RU2531277 C2 RU 2531277C2 RU 2011123484/04 A RU2011123484/04 A RU 2011123484/04A RU 2011123484 A RU2011123484 A RU 2011123484A RU 2531277 C2 RU2531277 C2 RU 2531277C2
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glycerol
catalyst
metal
acrolein
characterized
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RU2011123484/04A
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RU2011123484A (en
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Виржини БЕЛЛИЕР-БАКА
Стефан ЛОРИДАН
Жан-Марк МИЛЛЕ
Паскалин ЛОРИОЛЬ-ГАРБЕ
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Адиссео Франс С.А.С.
Сентр Насьональ Де Ла Решерш Сьентифик
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20Vanadium, niobium or tantalum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90Regeneration or reactivation
    • B01J23/92Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12Treating with free oxygen-containing gas
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/58Recycling
    • Y02P20/584Recycling of catalysts

Abstract

FIELD: chemistry.
SUBSTANCE: invention relates to an improved method of obtaining acrolein from glycerol. Dehydration of glycerol is carried out in the presence of a catalyst based on zirconium oxide, consisting at least of: a) mixed zirconium oxide and at least of one metal M, where the said metal is selected from niobium and vanadium, b) zirconium oxide and at least one metal M oxide, where the said metal is selected from niobium, tantalum and vanadium, c) silicon oxide and mixed zirconium oxide and at least one metal M, where the said metal is selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon, d) titanium oxide, mixed zirconium oxide and at least one metal M, where the said metal is selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon. The invention also relates to a method of obtaining 3-(methylthio)propionic aldehyde from acrolein and to application of a catalyst, selected from the catalysts a), b), c) or d) for conversion of glycerol into acrolein.
EFFECT: method makes it possible to obtain acrolein by catalytic dehydration of glycerol in the presence of catalyst, which provides conversion of all initial glicerine and at the same time can be easily regenerated during short time without losing activity and selectivity and possesses a long service term.
13 cl, 4 dwg, 5 tbl, 18 ex

Description

The present invention relates to a catalytic method for the production of acrolein by dehydration of glycerol or glycerol and to the application of this method.

By glycerol is meant refined or crude glycerol, preferably derived from biomass, in particular highly purified glycerol or partially purified glycerol. Purified glycerol has a purity greater than or equal to 98%, and it is obtained by distillation of glycerol. Crude or only partially purified glycerol can be presented as a solution in methyl alcohol if it is obtained, for example, by transesterification of triglycerides, as described below.

By glycerin is meant, in particular, natural glycerin obtained by hydrolysis of vegetable oils and / or animal fats, or synthetic glycerin obtained from petroleum, more or less refined or refined, or crude, with a concentration of from 80 to 85%. Thus, in the further description, it is mainly a question of the chemical conversion of glycerol or glycerol derived from biomass, but the present invention, of course, is not limited to this, and its scope extends to all varieties of glycerol or glycerol, regardless of the source of production and degree of purity.

The depletion of fossil energy sources leads industrial production to the need to use renewable raw materials derived from biomass to produce fuel. In this regard, the fuel produced from vegetable or animal oil is biological diesel fuel.

This product is known as “green” because of a very acceptable balance of CO 2 compared to fossil energy sources. Diester® (EMVH, Esters Methyliques d'Huiles Vegetales - methyl esters of vegetable oils) is a biological diesel fuel produced by transesterification of triglycerides contained in oily liquids by methanol, in particular in vegetable oils such as palm, rapeseed and sunflower. With this transesterification carried out by the processes described, approximately 100 kg of glycerol per ton of Diester® is also formed. The non-lipid part of the raw materials used, oilcake, is mainly used in animal feed.

Such biological diesel fuel is used in a mixture with gas oil. EU Directives 2001/77 / EC and 2003/30 / EC, which will come into force in the near future, include the inclusion of 7% in diesel fuel in 2010, and 10% Diester® by 2015. Such a significant increase in the amount of produced biological diesel fuel will lead to a significant amount of glycerol, amounting to several hundred thousand tons per year.

About 1,500 different uses of glycerol have already been proposed. Here are some examples of these that are present in many very different recipes:

hydrates in pharmacy (in suppositories and syrups) or in cosmetology as part of moisturizers, glycerin soaps, toothpastes, solvents in the food industry, plasticizers or lubricants in the chemical industry.

These applications will be clearly insufficient to utilize the amount of glycerol obtained in the production of biodiesel, and the glycerol market (soap, pharmacy, etc.), despite its expansion, will be unable to utilize all surpluses. Thus, it is extremely important to find new applications that allow the disposal of very significant amounts of glycerol.

Bearing in mind this urgent need, in recent years a number of ways out of the situation have been investigated (see M. Pagliaro et al., Angew. Chem. Int. Ed. (2007) 46, 4434-4440, M. Pagliaro, M. Rossi : The Future of Glycerol, RSC Publishing, Cambridge (2008)), including, inter alia, the following six disposal routes:

- conversion to 1,3-propanediol and 1,2-propanediol, used, in particular, as starting monomers for the synthesis of polyesters and polyurethanes,

- conversion to monoesters for the production of lubricants,

- conversion to polyglycerols used as food additives, emulsifiers,

- conversion to acrolein (by dehydration) and acrylic acid (by dehydration and oxidation),

- direct disposal as animal feed additives.

Acrolein and acrylic acid are traditionally produced by the controlled oxidation of propylene in the gas phase with atmospheric oxygen in the presence of catalysts based on molybdenum and / or bismuth oxides. Thus obtained acrolein can either be directly involved in the two-stage process for the production of acrylic acid, or used as an intermediate product of synthesis. Thus, the production of these two monomers is directly related to propylene, which is mainly obtained by steam cracking or catalytic cracking of petroleum fractions.

The market for acrolein, one of the simplest unsaturated aldehydes, and acrylic acid is huge, as these monomers are part of numerous mass-produced products.

In addition, acrolein, being due to its structure a highly reactive substance, finds numerous applications, in particular, as an intermediate in the synthesis of other products. For example, it is used in the synthesis of D, L-methionine and its hydroxyacalogue - 2-hydroxy-4-methylthiobutanoic acid (HMTBA, HMTBA). These feed additives are widely used because they are part of feed improvers necessary for the growth of animals (poultry, pigs, ruminants, fish, etc.). In some cases, it can be useful for increasing or even maintaining existing production capacities, expanding range of suitable raw materials. Thus, it seems very useful to increase the production of acrolein, while reducing dependence on propylene as a resource obtained from oil.

The objective of the present invention is the creation of powerful, active, selective and regenerated catalysts that allow you to get acrolein directly from glycerol or from glycerol, in particular obtained from biomass, in accordance with the reaction:

HO-CH 2 -CH (OH) -CH 2 -OH → CH 2 = CH-CHO + 2H 2 O

This alternative also provides a competitive method for the synthesis of acrolein, independent of propylene as an oil resource, from other, renewable raw materials.

This possibility is especially promising for the synthesis of methionine and its analogues, such as its hydroxy analog (HMTBA), directly from biomass.

The present invention also relates to the use of this reaction for the synthesis of 3-methylthiopropionic aldehyde, 2-hydroxy-4-methylthiobutyronitrile (HMTBN), methionine and its analogues, such as 2-hydroxy-4-methylthiobutanoic acid (HMTBK), esters of HMTBA, such as isopropyl ether; 2-oxo-4-methylthiobutanoic acid from acrolein.

Methionine, GMTBK, its esters and analogues are used in animal fattening and in industrial synthesis processes. Acrolein is usually obtained by oxidizing propylene and / or propane. The oxidation of propylene to acrolein with air in the presence of water vapor is partial and the resulting acrolein-based crude product also contains unreacted propylene and propane, water and oxidation by-products such as acids, aldehydes and alcohols.

Glycerol (also called glycerin), has long been known as a source of acrolein (thermal conversion). This substance is widely distributed in nature in the form of esters (triglycerides), in particular in the composition of all oils, as well as animal and vegetable fats, which makes it a reagent, available in large quantities and therefore industrially applicable. It is well known that glycerol decomposes with the formation of acrolein when heated to temperatures above 280 ° C. This low-selective reaction is accompanied by the formation of numerous by-products, in particular acetic aldehyde, hydroxyacetone, as well as products of the complete oxidation of CO, CO 2 . Therefore, it is necessary to control the reaction of the conversion of glycerol to acrolein in order to avoid excessive consumption of this resource and the need for additional energy-intensive purification of the obtained acrolein. In addition, by-products, mostly aromatic, often cause the formation of a coke layer on the surface of the catalyst, which over time leads to spoilage of the catalyst, and often it is necessary to regenerate the catalyst to restore satisfactory catalytic activity.

Many researchers in the fundamental and applied fields have studied this reaction. In particular, it was proposed to use supercritical water as a reaction medium. The use of a supercritical solvent on an industrial scale is difficult in a continuous process due to particularly sophisticated equipment, in particular autoclaves that operate at very high pressures. On the contrary, the implementation of continuous or intermittent production is possible if a productive, selective and stable catalyst system is offered.

Due to the growing interest in such a chemical alternative, many studies are described in the literature related to the use of 2 catalytic systems based on immobilized phospho- or silicon-tungsten heteropoly acids, mixed oxides and zeolites, applicable in continuous or intermittent production methods in the liquid or gas phase.

Thus, documents WO-A-2006087083 and WO-A-2006087084 describe a method for the catalytic dehydration of glycerol to produce acrolein in the gas phase in the presence of molecular oxygen and a strongly acid catalyst selected from zeolites, Nafion (Nation *), metal oxides selected from aluminum, zirconium, titanium, niobium, tantalum, silicon, impregnated with acid groups in the form of sulfate, borate, tungstate, silicate and phosphate groups.

WO-A-2007132926 describes a process for converting glycerol to acrolein in the presence of a catalyst selected from acidic crystalline metal silicates, such as MFI or BEA structure type zeolites containing silicon and an element, preferably selected from Al, Fe and Ga.

In contrast to the known methods according to the described, a method for producing acrolein from glycerol or from glycerol by catalytic dehydration of glycerol in the presence of a catalyst, which, providing the conversion of all of the original glycerol, at the same time can be very easily regenerated and has a long service life, is proposed. The authors of the present invention have discovered that such properties are possessed by a zirconia-based catalyst consisting of at least:

a) a mixed zirconium oxide and at least one metal M, wherein said metal is selected from niobium, tantalum and vanadium,

b) zirconium oxide and at least one metal oxide M, wherein said metal is selected from niobium, tantalum and vanadium,

c) silicon oxide and a mixed zirconium oxide and at least one metal M, wherein said metal is selected from tungsten, cerium, manganese, niobium, titanium, vanadium and silicon,

d) silica and mixed zirconium oxide and at least one metal oxide M, wherein said metal is selected from tungsten, cerium, manganese, niobium, tantalum, vanadium and titanium,

e) titanium oxide and mixed zirconium oxide and at least one metal M, wherein said metal is selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon.

e) titanium oxide and mixed zirconium oxide and at least one metal oxide M, wherein said metal is selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon.

Thus, the present invention relates to a method for producing acrolein from glycerol or glycerol in the presence of a catalyst, as defined above, and the use of such a catalyst for converting glycerol or glycerol to acrolein. The catalyst according to the present invention provides a controlled conversion of glycerol or glycerol to acrolein, that is, does not contribute to its further conversion to acrylic acid. For this purpose, the preferred catalyst according to the present invention does not contain molybdenum oxide and / or copper oxide, or does not contain these oxides in a significant mass fraction with respect to each of the other oxides constituting the catalyst.

Therefore, the present invention relates to the use of at least one of the catalysts a), b), c), d), e) and e), as defined above, for the conversion of glycerol or glycerol to acrolein.

The catalyst can be obtained in various ways (by co-precipitation, hydrothermal synthesis, etc.). An effective method has been described in the literature (Kantcheva et al., Catalysis Communications (2008), 9 (5), p.874-879 and in patents FR 2907444 and FR 2907445).

The above catalyst may also correspond to the preferred characteristics given below, considered separately or in combination: the catalysts a) to e) consist only of the above oxides and mixed oxides, with at least one oxide, mixed or not, in the composition of the catalysts from a) to e) immobilized; the molar ratio Zr / sum of other elements constituting said catalysts a) to e) other than Zr, that is, selected from Si, Ti and M, is from 0.5 to 200, more preferably from 1 to 100. As indicated above, the catalyst according to the present invention is advantageously characterized in that it can easily be regenerated without reducing the yield of the dehydration reaction and selectivity for acrolein.

The reaction according to the present invention can be carried out in the gas or liquid phase, preferably in the gas phase. When carrying out the reaction in the gas phase, the method can be carried out using various technologies, namely in a fixed bed, in a fluidized bed or in a circulating fluidized bed. In the first two embodiments, in a fixed bed or in a fluidized bed, the regeneration of the catalyst can be separated from the catalytic reaction. The regeneration can be carried out ex situ by conventional methods, such as burning in air or in a gas mixture containing molecular oxygen. In accordance with the method, in accordance with the present invention, regeneration can be carried out in situ, since the temperature and pressure at which regeneration occurs are close to the reaction conditions carried out by this method.

In the liquid phase, the reaction can be carried out in a conventional reactor for liquid phase reactions on a solid catalyst, as well as in a catalytic distillation reactor, taking into account the significant difference in the boiling point of glycerol (290 ° C) and acrolein (53 ° C). It also makes sense to consider the implementation of the reaction in the liquid phase at a relatively low temperature, which provides continuous distillation of the produced acrolein, thereby limiting the subsequent reaction of the destruction of acrolein.

The experimental reaction conditions in the gas phase are temperatures from 250 to 400 ° C and pressures from 1 to 10 bar. In the liquid phase, the reaction is carried out at a temperature of from 150 to 350 ° C and a pressure in the range from 3 to 70 bar.

Another advantage of the method according to the present invention is that the starting glycerol or glycerin can be presented in pure or partially purified form or in the form of a solution, in particular aqueous. An aqueous glycerol solution is preferably used. In an aqueous solution, the concentration of glycerol is preferably at least 1%, it is better if it is from 10 to 50 wt.% And preferably from 15 to 30 wt.% In the reactor. The glycerol concentration should not be too high in order to avoid adverse reactions that reduce the yield of acrolein, such as the formation of glycerol esters or acetalization of the produced acrolein with unconverted glycerol. On the other hand, the glycerol solution should not be too diluted, taking into account the inevitable energy consumption caused by the evaporation of glycerol. In all cases, the concentration of the glycerol solution can easily be brought to the desired by partially or completely utilizing the water obtained during the reaction.

Energy optimization in the framework of synthesis may consist in the utilization of heat at the outlet of the reaction to evaporate the glycerol stream entering the reactor.

Another object of the present invention is a method for producing from acrolein 3- (methylthio) propionic aldehyde, 2-hydroxy-4-methylthiobutyronitrile (HMTBN), methionine, 2-hydroxy-4-methylthiobutanoic acid (HMTBA), the latter esters, in particular isopropyl ether, and 2-oxo-4-methylthiobutanoic (OMTBA) acid, according to which acrolein is prepared by the method described above. When compared with the conventional method for producing acrolein by the controlled oxidation of propylene, the acrolein obtained by the above method may contain impurities that differ from the usual ones, both in terms of their quantity and their nature. Thus, to obtain acrylic acid, methionine or its hydroxy analogue, it is possible to provide for the preliminary purification of acrolein by methods known to those skilled in the art.

Acrolein obtained according to the present invention, directly or after purification, is reacted with methyl mercaptan to obtain 3- (methylthio) propionic aldehyde (MTPA). In the next step, MTPA is treated with hydrocyanic acid to give 2-hydroxy-4- (methylthio) butyronitrile (HMTBN). After the synthesis of HMTBN, various stages of the synthesis lead to the production of methionine, its hydroxy analogue (HMTBA), esters of the latter or its oxo analogue (OMTBA). All stages, starting from the synthesis of acrolein, are well known to specialists.

Further, the present invention will be described in more detail and illustrated by the following examples and figures without limiting the scope of the claims.

The Figure 1 presents the dependence of the conversion of glycerol and selectivity for acrolein on time for each of the catalysts A, B, C and D described in examples 1, 7, 8 and 9, respectively; catalysts A and B correspond to the present invention, catalysts C and D correspond to the prior art. The time indicated for each point is the end time of the sampling, corresponding to the capture within one hour. The reaction conditions and the methods used to calculate the conversion and selectivity for acrolein are described below.

The designations in this figure are as follows:

- the conversion of glycerol on the catalyst A (□), B (Δ), C (◇) or D (o)

- selectivity for acrolein on catalyst A (■), B (▲), C (♦) or D (•)

Figure 2 illustrates the conversion of glycerol and selectivity for acrolein for catalyst A according to the present invention before and after regeneration in an air stream.

The designations in this figure are as follows:

- glycerol conversion on a fresh catalyst (Δ) and on a regenerated catalyst (▲)

- selectivity for acrolein on a fresh catalyst (□) and on a regenerated catalyst (■)

The Figure 3 presents a comparison of the conversion of glycerol and the selectivity of this conversion for acrolein in time for each of the catalysts A ', B and D described in examples 2, 8 and 9, respectively; catalyst A ′ corresponds to the present invention, catalysts B and D correspond to the prior art.

The designations in this figure are as follows:

- the conversion of glycerol on the catalyst A '(♦), D (•) or C (□)

- selectivity for acrolein on the catalyst A '(■), D (×) or C (▲)

Figure 4 illustrates the conversion of glycerol and acrolein selectivity for catalyst A 'according to the present invention before and after regeneration in an air stream.

The designations in this figure are as follows:

- conversion of glycerol on a fresh catalyst (Δ) and on a regenerated catalyst (▲)

- selectivity for acrolein on a fresh catalyst (□) and on a regenerated catalyst (•)

The time indicated for each point is the end time of the sampling, corresponding to the capture within one hour. The reaction conditions and the methods used to calculate the conversion and selectivity for acrolein are described below.

The glycerol dehydration reaction was carried out on the indicated catalysts at atmospheric pressure in a direct reactor with a fixed bed with a diameter of 18 mm. The reactor was placed in a furnace, which allowed the catalyst to maintain the temperature necessary for the reaction, which was 300 ° C. The volume of catalyst loaded into the reactor was 4.5 ml, with a layer thickness of about 1.8 cm. A 20% (wt.) Aqueous solution of glycerol was fed to the reactor at a rate of 3.77 g / h. The aqueous glycerol solution was evaporated using a C.E. M 15 (Controlled Evaporator Mixer) Bronkhorst * evaporator in a nitrogen stream of 75 ml / min. The approximate molar ratio glycerol / water / nitrogen was 2.3 / 46.3 / 51.4. The estimated contact time was about 1.9 s, which corresponds to a GHSV of 1930 h -1 . Contact time was determined as follows:

Contact time = Catalyst volume × P atm / (total molar flow rate × Temperature × R),

where P atm = 101325 Pa, Temperature = 25 ° C, and the total molar flow rate = molar flow rate of glycerol + molar flow rate of water + molar flow rate of inert gas.

At the end of the reaction, the products were condensed. Two condensation systems were used. In examples 10, 11, 12, 16, 17, and 18, a system with three traps mounted in series was used. The first trap contained a certain amount of water and was cooled with crushed ice. The other two traps contained ethanol and were cooled in a cryostat at -25 ° C. In examples 13, 14 and 15, a simple trap was used with a certain mass of water, which was cooled with crushed ice. The duration of condensation was 1 hour, and the supply flow was not interrupted when changing traps.

The resulting products were analyzed chromatographically, each sample was analyzed twice.

The main reaction products were analyzed by gas chromatography in a capillary column (Nukol, 30 m × 0.53 mm) on a Shimadzu 2014 chromatograph equipped with an FID detector. In this case, acrolein, acetic aldehyde, acetone, propionic aldehyde, hydroxypropanone, acetic acid, allyl alcohol and phenol were quantified.

The remaining glycerol was quantified by gas chromatography on a Helwett Packard chromatograph equipped with an FID detector and a capillary column (Carbowax or ZBwax, 30 m × 0.32 mm).

Glycerol conversion, acrolein selectivity, and yields of various products were determined as follows:

Glycerol conversion (%) = 100 × (1 - residual number of moles of glycerol / initial number of moles of glycerol)

Acrolein selectivity (%) = 100 × (number of moles of produced acrolein / number of moles of glycerol reacted)

Yield X (%) = K × 100 × number of moles of produced X / initial number of moles of glycerol

In this case, K = 1, if X is acrolein, acetone, hydroxypropanone, propanal or acrylic alcohol; K = 2/3 if X is acetic aldehyde or acetic acid and K = 2 if X is phenol.

Example 1: Preparation and Characterization of Catalyst A

The catalyst of the present invention based on zirconium and niobium oxides was prepared from hydrate of zirconium oxide and ammonium oxaloniobate (NH 4 ) (C 2 O 4 ) 2 NbO. × H 2 O (Aldrich, 99.99%). Zirconia hydrate was prepared by coprecipitation of a solution of zirconium oxonitrate ZrО (NO 3 ) 2. × Н 2 O (Aldrich, 99%) and 28% ammonia solution at pH = 8.8.

Ammonium oxaloniobate was dissolved in permuted water, acidified with concentrated HNO 3 to a pH of ~ 0.5 and heated to 45 ° C. After cooling to ambient temperature, zirconia hydrate with a ZrO 2 / Nb 2 O 5 molar ratio of 3: 1 was added; before that, the hydration level of zirconia hydrate was determined by thermogravimetric analysis. After 24 hours, with stirring, the mixture was filtered, and the precipitate was calcined in a stream of air at 600 ° C. The specific surface of this catalyst was 40 m 2 / g. The specific surfaces of the powders were measured by the BET method (Brunauer-Emmet-Teller) at -196 ° C using a Micromeritics ASAP 2020 apparatus. The powders were previously desorbed at 300 ° C for 3 hours in a vacuum of 5 × 10 -5 mbar. The content of niobium and zirconia in the various catalysts prepared was determined by the ICP-OES method (inductively coupled plasma optical emission spectroscopy optical inductively coupled plasma emission spectrometry). The molar ratio of Zr / Nb in catalyst A, calculated based on the analyzes performed, was 9.3.

Example 2: preparation and characterization of catalyst A '

The catalyst of the present invention based on zirconium and niobium oxides was prepared in accordance with the procedure described in the literature (Kantcheva et al., Catalysis Communications (2008), 9 (5), p874-879) by impregnating zirconium oxide hydrate.

Zirconium hydrate was prepared by coprecipitation of a solution of zirconium zirconium ZrC (NO 3 ) 2. × H 2 O (Aldrich, 99%) and 28% ammonia solution. The precursor Nb (V), (NH 4 ) (C 2 O 4 ) 2 NbO. × H 2 O (Aldrich, 99.99%) was added with stirring to a 35% solution of hydrogen peroxide (Sigma Aldrich), acidified to pH = 0.5 by adding HNO 3 , concentrated and heated to 50 ° C. The molar ratio of H 2 O 2 / oxalate was 13/1. The solution was heated for 1 hour at 50 ° C, then cooled to ambient temperature. Then zirconia hydrate was added to the ZrO 2 : Nb 2 O 5 = 6: 1 ratio, the hydration level of zirconium hydrate was previously determined by thermogravimetric analysis. The mixture was left under stirring for 24 hours at ambient temperature, after which the liquid phase was distilled off under reduced pressure at t ° <70 ° C. The resulting residue was calcined in an air stream at 600 ° C.

The specific surface of this catalyst was 51 m 2 / g. The specific surface of the powders was measured by the BET method (Brunauer-Emmet-Teller) at -196 ° C using a Micromeritics ASAP 2020 apparatus. The powders were previously desorbed at 300 ° C for 3 hours in a vacuum of 5 × 10 -5 mbar. The content of niobium and zirconium in different prepared catalysts was determined by the ICP-OES method. The molar ratio of Zr / Nb in this catalyst was 3.3.

Example 3: Preparation and Characterization of Catalyst E

The catalyst according to the present invention based on zirconium and niobium oxides was prepared in accordance with the procedure described in the literature (Kantcheva et al., Catalysis Communications (2008), 9 (5), pp. 874-879), by impregnating zirconium oxide hydrate with a solution, containing mixed ammonium oxalate and niobium.

The precursor Nb (V), (NH 4 ) (C 2 O 4 ) 2 NbO. × H 2 O (Aldrich, 99.99%) was added with stirring to a 35% solution of hydrogen peroxide (Sigma Aldrich), acidified to pH = 0.5 by adding concentrated HNO 3 and heated to 50 ° C. The molar ratio of H 2 O 3 / oxalate was 13/1.

The solution was heated for 1 hour at 50 ° C, then cooled to ambient temperature.

Next, zirconia hydrate was added, previously prepared by co-precipitation of a solution of zirconium zirconium ZrO (NO 3 ) 2. × H 2 O (Aldrich, 99%) and 28% ammonia in the ratio ZrO 2 : Nb 2 O 5 = 6: one. The mixture was allowed to stir for 24 hours at ambient temperature, after which the liquid phase was distilled off under reduced pressure at t ° <70 ° C. The resulting residue was calcined in an air stream at 600 ° C.

The specific surface area of this catalyst, determined as in the case of catalyst A, was 39 m 2 / g. The content of niobium and zirconium in various prepared catalysts was determined by the ICP-OES method. The molar ratio of Zr / Nb in this catalyst was 3.7.

Example 4: Preparation and Characterization of Catalyst F

The catalyst according to the present invention based on zirconium, niobium and vanadium oxides. The vanadium precursor was prepared from NH 4 VO 3 (Sigma, ACS Reagent 99.7%) in the following way:

Ammonium metavanadate was dissolved in a 9% hydrogen peroxide solution containing oxalic acid (Aldrich, 99%). The molar ratio of oxalic acid / NH 4 VO 3 was 1.3. After 1 hour stirring at ambient temperature, the solution was evaporated under reduced pressure to give a blue powder. The vanadium oxide content in this substance was determined thermogravimetrically.

The niobium precursor is mixed niobium-ammonium oxalate (NH 4 ) (C 2 O 4 ) 2 NbO × H 2 O (Aldrich, 99.99%) and the zirconia hydrate obtained as described in Example 1 was introduced into an aqueous solution acidified with concentrated HNO 3 (pH <0.5), in a molar ratio of Zr / Nb / V, equal to 72/22 / 3.2. After 24 hours with stirring, the reaction mixture was filtered and the precipitate was calcined in an air stream at 600 ° C.

The specific surface area of this catalyst, determined in the same way as in the case of catalyst A, was 48 m 2 / g. The content of niobium, vanadium and zirconium in the resulting catalyst was determined by the ICP-OES method. The molar ratio of Zr / Nb / V in this catalyst was 90.4 / 8.4 / 1.2.

Example 5: Preparation and Characterization of Catalyst G

The catalyst according to the present invention based on zirconium and tungsten with a silica additive. The preparation of this catalyst involves three steps. The first stage is the synthesis of zirconium oxide hydrate at pH = 8.8. The second stage consists in stabilizing the hydrate of zirconium oxide by silica particles (Nahas et al. - Journal of Catalysis 247 (2007), p51-60). Zirconium hydroxide was placed in a glass flask with an ammonia solution, the pH of which was adjusted to 11. The mixture was refluxed for 72 hours, then filtered and washed with permuted water. The last step was the exchange reaction between tungsten acid H 2 WO 4 (Aldrich, 99%) dissolved in hydrogen peroxide and zirconium hydroxide. Tungsten acid was dissolved in a 35% hydrogen peroxide solution at 60 ° C. The tungsten acid concentration in the solution was 0.04 M. Then the tungsten acid solution was cooled at room temperature and silica-doped zirconium hydroxide was gradually added. The resulting precipitate was filtered off and calcined in air at 650 ° C. Its specific surface was 40 m 2 / g. The content of tungsten, silicon and zirconium in the catalyst was determined by the ICP-OES method. The W / Si / Zr molar ratio in this catalyst was 4.7 / 1.4 / 93.9.

Example 6: synthesis of catalyst H

Catalyst H was prepared by the method described in example 1. The pH of the nitric acid solution in the case of catalyst H was selected so that it was slightly more acidic (pH <0.1). The resulting catalyst has a specific surface area of 57 m 2 / g and a molar ratio of Zr / Nb equal to 11.8.

Example 7: Preparation and Characterization of Catalyst B

The ZrTiSiW catalyst according to the present invention was prepared by Rhodia by the method described in patent FR 2907445 A. The specific surface area of this catalyst, defined as in the case of catalyst A, was 105 m 2 / g. The mass fraction of oxides in this catalyst was 54% ZrO 2 , 35% TiO 2 , 7.5% SiO 2 3.5% WO 3 .

Example 8: Preparation and characterization of catalyst C (corresponding to the prior art, for comparison)

Catalyst C is tungsten zirconia (89.5% ZrO 2 - 10.5% WO 3 ) synthesized by Daiichi Kigenso, vendor code: Z-1104. The specific surface area of this catalyst, determined in the same way as in the case of catalyst A, was 77 m 2 / g

Example 9: preparation and characterization of catalyst D (corresponding to the prior art, for comparison)

Catalyst D is zeolite H-ZSM-5 (Zeochem, ZEOcat PZ-2 / 50H). The specific surface area of this catalyst, determined as in the case of catalyst A, was 406 m 2 / g.

Example 10: Catalytic dehydration of glycerol to form acrolein: evaluation of catalysts A, B, C and D

Table 1 shows the performance achieved using catalysts A, B, C, and D after 6 hours of reaction.

Table 1 A (fig.) In (image) C (comp.) D (compare) Glycerol conversion one hundred one hundred 94 57 Acrolein Selectivity 66 69 64 65 Acrolein yield 66 69 60 37 Acetaldehyde yield 6.3 6.5 3.9 0.6 Propionaldehyde Output 3,1 5,4 2,8 1,6 Acetone yield 1.7 2.7 1,6 0,0 Allyl alcohol yield 0.1 0.5 0.5 0.2 Hydroxypropanone yield 5.8 3,1 6.1 3.0 Phenol yield 2.6 0.8 0.3 -

This table shows that with an equal volume of catalyst, only catalysts A and B (corresponding to the present invention) provide complete conversion of glycerol. In addition, the catalysts according to the present invention have better selectivity for acrolein, noticeable after 6 hours and even more pronounced after 50 hours with an acrolein yield of 70% for catalyst A and 80% for catalyst B.

Thus, catalysts A and B are more active and more selective than the catalysts corresponding to the prior art.

Example 11: Catalytic dehydration of glycerol with the formation of acrolein: change in the performance of catalysts A, B, C and D over time

The change in productivity of catalysts A, B, C and D depending on time, determined under the same conditions as in example 4, is presented in Figure 1.

Catalysts A and B (corresponding to the present invention) retain constant acrolein selectivity and a high degree of glycerol conversion for several days, in contrast to the prior art catalysts C and D, which are substantially deactivated after less than 24 hours.

Thus, catalysts A and B according to the present invention are more active, more selective for acrolein, and also more durable than the best of the catalysts disclosed in the prior art.

Example 12: Regeneration of catalyst A

After 143 hours of incubation of the reaction mixture at 300 ° C with stirring, Catalyst A according to the present invention was regenerated in a stream of air at 450 ° C for 2 hours (air flow 51 ml / min). After regeneration, the catalyst was tested under the same operating conditions as before regeneration.

The results obtained are presented in Figure 2. Regeneration in air at 450 ° C allowed the catalyst And to restore its original activity and return. Thus, the catalyst A according to the present invention can be regenerated in a short time without loss of activity and selectivity. Catalyst A is not only active and selective, but can also be easily and completely regenerated.

Example 13: Catalytic dehydration of glycerol with the formation of acrolein: a comparison of the catalytic properties of catalysts A ', D and C

Table 2 shows the performance characteristics obtained using catalysts A ', C, and D after 5 hours of reaction at 300 ° C.

table 2 A '(fig.) D (compare) C (comp.) Glycerol conversion one hundred 88 99 Acrolein Selectivity 46.8 38.8 45.6 Acrolein yield 47 44 46 Acetaldehyde yield 7.9 1.3 4.6 Propionaldehyde Output 14.3 3,5 8.9 Acetone yield 1.4 0 2.1 Allyl alcohol yield 0.9 0.5 0.5 Hydroxypropanone yield 3.4 4.8 5.8 Acetic acid yield 0.9 0.6 Phenol yield 3.4 0.2 1.3

This table shows that with an equal volume of catalyst, only catalyst A '(according to the present invention) provides the complete conversion of glycerol. In addition, catalyst A ′ has better selectivity for acrolein. Thus, the catalyst A 'is more active and more selective than the catalysts corresponding to the prior art.

Example 14: Catalytic dehydration of glycerol with the formation of acrolein: change in the productivity of catalysts A ', D and C over time

The change in productivity of the catalysts A ', D and C depending on time is shown in Figure 3.

Catalyst A ′ (corresponding to the present invention) maintains an almost constant acrolein selectivity and a high conversion of glycerol in the reaction stream for a week, in contrast to the prior art catalysts C and D, which are substantially deactivated after less than 24 hours.

Thus, the catalyst A 'of the present invention is more active, more selective for acrolein, and also more durable than the best catalysts claimed in the prior art.

Example 15: Regeneration of the catalyst A '

After 183 hours of working in the reaction mixture, catalyst A ′ according to the present invention was regenerated in an air stream at 450 ° C. for 1 hour (air flow 51 ml / min). After regeneration, the catalyst was tested under the same operating conditions as before regeneration.

The results are presented in figure 4.

Regeneration in air at 450 ° C allowed the catalyst A 'to restore its original activity and return. Thus, the catalyst A 'according to the present invention can be regenerated in a short time without loss of activity and selectivity. Catalyst A is not only active and selective, but can also be easily and completely reduced.

Example 16: Catalytic dehydration of glycerol to form acrolein: evaluation of catalysts E and F (according to the present invention)

Table 3 shows the characteristics of the catalysts E and F

Table 3 E F sampling hour 5 twenty 48 72 95 6 24 Glycerol conversion 10 98 97 94 90 one hundred 94 Acrolein Selectivity 60 72 73 72 71 fifty 51 Acrolein yield 60 71 71 68 63 fifty 48 Acetaldehyde yield 4.9 3,1 2.6 2.6 2,5 8 5.5 Propionaldehyde Output 6.8 4.8 3.9 3.9 3.8 5.8 four Acetone yield 1.9 1.7 one 1,1 0.9 4.1 3.2 Allyl alcohol yield 0.6 0.7 0.7 0.7 0.7 3.2 4.4 Hydroxypropanone yield 5.1 12,2 13.5 13.1 12,4 3,1 7.7 Phenol yield 1.9 0.9 0.5 0.5 0.3 1.3 0.7

Example 17: Catalytic dehydration of glycerol to form acrolein: evaluation of catalyst G (according to the present invention)

Table 3 shows the characteristics of the catalyst.

Table 4 sampling hour four 23 42 Glycerol conversion 98 96 87 Acrolein Selectivity 68 80 83 Acrolein yield 67 77 72 Acetaldehyde yield 4.2 3,5 2,4 Propionaldehyde Output 3,1 2,4 1,6 Acetone yield 1,2 1.3 0.9 Allyl alcohol yield 0.7 0.9 0.6 Hydroxypropanone yield 5.2 10.9 9.7 Phenol yield 0.8 0.2 -

Example 18: Obtaining acrolein from crude glycerol using catalyst H

The productivity of the catalyst H was determined using a crude technical solution of glycerol with a concentration of 82 wt.%. This glycerin contained up to 15% methyl alcohol. As in the previous examples, the volume of catalyst in the reactor was 4.5 ml, the nitrogen flow rate was 74.5 ml / min, and the reaction temperature was 300 ° C. The flow rate of a 20% (by weight) aqueous glycerol solution was 3.77 g / h. The molar ratio glycerol / water / nitrogen was 1.9 / 46.5 / 51.6. The results are presented in table 5.

Table 5 selection end time 8 26 51 76 one hundred one Glycerol conversion one hundred one hundred one hundred one hundred 99 9 Selectivity by 56 71 73 73 73 7 acrolein R Acrolein yield 56 71 73 73 72 6 8 Acetaldehyde yield 7.4 6.2 5,4 4.6 3.9 2 Propionaldehyde Output 5.2 3.6 3,1 2,8 2,4 one Acetone yield 2.0 2.0 1.4 1,2 0.9 0 Allyl alcohol yield 0.9 1.3 1.4 1,5 1,5 one Hydroxypropanone yield 1.9 11.1 14.5 15.6 17.9 one 7 Phenol yield 5,0 1.7 0.9 0.6 0.4 0

The presence of a significant amount of methyl alcohol does not impair the performance of the catalyst of the present invention.

Claims (13)

1. The method of producing acrolein from glycerol, characterized in that the dehydration of glycerol is carried out in the presence of a catalyst based on zirconium oxide, consisting of at least:
a) a mixed zirconium oxide and at least one metal M, wherein said metal is selected from niobium, tantalum and vanadium,
b) zirconium oxide and at least one metal oxide M, wherein said metal is selected from niobium, tantalum and vanadium,
c) silicon oxide and a mixed zirconium oxide and at least one metal M, wherein said metal is selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon,
d) titanium oxide, mixed zirconium oxide and at least one metal M, wherein said metal is selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon.
2. The method according to claim 1, characterized in that the catalyst consists of at least: a) a mixed zirconium oxide and at least one metal M and b) zirconium oxide and at least one metal oxide M.
3. The method according to claim 1 or 2, characterized in that at least one of the oxides in the composition of these catalysts from a) to g) is immobilized.
4. The method according to claim 1, characterized in that the molar ratio Zr / sum of elements Si, Ti and M other than Zr is from 0.5 to 200.
5. The method according to claim 4, characterized in that the molar ratio is from 1 to 100.
6. The method according to claim 1, characterized in that the glycerol is in an aqueous solution with a concentration of not less than 1 wt.%.
7. The method according to claim 6, characterized in that the concentration of an aqueous solution of glycerol is from 10 to 50 wt.%.
8. The method according to claim 1, characterized in that the catalyst is regenerated.
9. The method of obtaining 3- (methylthio) propionic aldehyde from acrolein, characterized in that acrolein is obtained by the method according to any one of claims 1 to 8.
10. The method according to claim 1 or 9, characterized in that the dehydration reaction is carried out in the gas phase.
11. The method according to claim 10, characterized in that the dehydration reaction is carried out in a fixed-bed reactor, with a fluidized bed or with a circulating fluidized bed.
12. The method according to claim 1 or 9, characterized in that the dehydration reaction is carried out in the liquid phase.
13. The use of a catalyst consisting of at least one catalyst a), b), c) or d), according to any one of claims 1 to 5 and, possibly, 8 for the conversion of glycerol to acrolein.
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FR2966456B1 (en) * 2010-10-26 2013-03-15 Adisseo France Sas Process for obtaining acrolein by catalytic dehydration of glycerol or glycerin
FR2997398B1 (en) 2012-10-30 2014-11-21 Adisseo France Sas Process for preparing acrolein from glycerol
FR3001728B1 (en) * 2013-02-04 2015-11-13 Adisseo France Sas Process for preparing olefin by catalytic conversion of at least one alcohol
KR101616528B1 (en) * 2013-07-16 2016-04-28 주식회사 엘지화학 Catalyst for dehydration of glycerin, method of preparing the same, and preparing method of acrolein
WO2015168683A1 (en) 2014-05-02 2015-11-05 University Of Tennessee Research Foundation Novel glycerol dehydration methods and products thereof
CN104892382B (en) * 2015-05-28 2017-08-11 珠海凯美科技有限公司 The method that glycerine liquid phase oxidation prepares methacrylaldehyde
KR102052708B1 (en) * 2015-12-22 2019-12-09 주식회사 엘지화학 Catalyst for dehydration of glycerin, preparing method thereof and production method of acrolein using the catalyst
KR102044428B1 (en) * 2015-12-23 2019-12-02 주식회사 엘지화학 Process for preparing acrylic acid from glycerin

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